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WO2018186002A1 - Composition de résine, son utilisation et son procédé de production - Google Patents

Composition de résine, son utilisation et son procédé de production Download PDF

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Publication number
WO2018186002A1
WO2018186002A1 PCT/JP2018/002183 JP2018002183W WO2018186002A1 WO 2018186002 A1 WO2018186002 A1 WO 2018186002A1 JP 2018002183 W JP2018002183 W JP 2018002183W WO 2018186002 A1 WO2018186002 A1 WO 2018186002A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
resin composition
aromatic polycarbonate
mass
polycarbonate resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/002183
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English (en)
Japanese (ja)
Inventor
晃人 栗山
貴裕 大江
上田　賢司
浩平 清水
稲垣　靖史
靖俊 川手
新吾 一瀬
澤田　真一
尚人 森永
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sony Corp
Original Assignee
Sony Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sony Corp filed Critical Sony Corp
Priority to JP2019511070A priority Critical patent/JP7060013B2/ja
Priority to CN202210249663.1A priority patent/CN114634695A/zh
Priority to CN201880023460.2A priority patent/CN110506078B/zh
Publication of WO2018186002A1 publication Critical patent/WO2018186002A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters

Definitions

  • the present technology relates to a resin composition and a method for producing the resin composition.
  • Resin compositions containing polycarbonate resin are used in various fields such as exterior, electronic / electrical applications, optical disk substrates and the like.
  • the present situation is that further improvement in the performance of the resin composition containing the polycarbonate resin is desired as the application is expanded in the OA / copier field, the automobile field, the medical material field, and the like.
  • a glycol containing a dicarboxylic acid polycondensation component composed of one or more terephthalic acid components selected from the group consisting of terephthalic acid and terephthalic acid derivatives, and 40 mol% or more of 1,4-cyclohexanedimethanol
  • a transparent face plate for outdoor use characterized by comprising 60 to 80 parts by weight of a polyester resin obtained by polycondensation with a system polycondensation component and 40 to 20 parts by weight of a polycarbonate resin has been proposed (Patent Document 1). See).
  • a curable paint for polycarbonate resin containing a compound (A) having two or more (meth) acryloyl groups in the molecule, conductive fine particles (B) and an organic solvent (C), wherein the organic Proposed curable coating for polycarbonate resin, containing at least a compound (C-1) having a solubility parameter of 8.0 to 10.0 (cal / cm 3 ) 1/2 as solvent (C) (See Patent Document 2).
  • Patent Documents 1 and 2 may not be able to further improve the resin physical properties.
  • the main object of the present technology is to provide a resin composition having excellent resin properties and a method for producing a resin composition having excellent resin properties.
  • the present technology provides a resin composition comprising 100 parts by mass of an aromatic polycarbonate resin and 0.01 to 5.0 parts by mass of a polyurethane resin having a crosslinked structure, wherein the polyurethane resin is a cured resin.
  • the average particle size of the polyurethane resin powder having the crosslinked structure may be 0.5 mm to 1.5 mm.
  • the ratio of the particle diameter of the polyurethane resin powder having the crosslinked structure to 0.5 mm to 1.5 mm may be 70% or more with respect to the total powder of the polyurethane resin having the crosslinked structure.
  • the polyurethane resin having the crosslinked structure may be obtained from a reaction between a polyester polyol and a polyisocyanate.
  • the mass ratio of the polyester polyol and the polyisocyanate may be 100: 50 to 100: 200.
  • the polyester polyol may have a hydroxyl value of 30 to 300.
  • the polyester polyol may have a polystyrene-equivalent weight average molecular weight of 10,000 or more and 500,000 or less.
  • the polyisocyanate may have two or more isocyanate groups.
  • An organic sulfonic acid and / or an organic sulfonic acid metal salt compound may further be included in an amount of 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin.
  • the organic sulfonic acid metal salt compound may have a polystyrene equivalent weight average molecular weight of 30,000 or more.
  • the organic sulfonic acid metal salt compound may contain a sulfonic acid metal base, and the content of the sulfonic acid metal base may be 0.1 to 10 mol%.
  • the aromatic polycarbonate resin may contain a recycled polycarbonate resin, and the content of the recycled polycarbonate resin may be 1 to less than 100% by mass with respect to the total mass of the aromatic polycarbonate resin.
  • the polyurethane resin having the crosslinked structure is added to 100 parts by mass of the aromatic polycarbonate resin, and the aromatic polycarbonate resin and the crosslinked structure are added. It may be obtained by kneading with a polyurethane resin.
  • a polyurethane resin having a crosslinked structure is added to 100 parts by mass of the aromatic polycarbonate resin, and the aromatic polycarbonate resin and the polyurethane resin having the crosslinked structure are added.
  • a method for producing a resin composition comprising kneading.
  • the method for producing a resin composition according to the present technology may include producing a polyurethane resin having the crosslinked structure by reacting a polyester polyol and a polyisocyanate.
  • the physical properties of the resin can be improved.
  • the effect described here is not necessarily limited, and may be any effect described in the present technology.
  • the present technology relates to a resin composition including an aromatic polycarbonate resin and a polyurethane resin having a crosslinked structure, which have improved resin physical properties. More specifically, the present technology improves surface physical properties such as solvent resistance, chemical resistance, and scratch resistance without coating the surface with a coating material, and is excellent in the inherent resistance of an aromatic polycarbonate resin.
  • the present invention relates to a resin composition having improved fluidity without impairing mechanical properties such as impact properties.
  • the present technology also relates to a method for producing the resin composition.
  • a resin composition containing a polycarbonate resin is excellent in heat resistance, impact resistance, transparency, and the like.
  • a resin composition containing a polycarbonate resin for example, an aromatic polycarbonate resin
  • improvement of surface properties such as fluidity, solvent resistance, and chemical resistance of a resin composition containing a polycarbonate resin is desired.
  • PET polyethylene terephthalate resin
  • PBT polybutylene terephthalate resin
  • the present technology provides a resin composition comprising 100 parts by mass of an aromatic polycarbonate resin and 0.01 to 5.0 parts by mass of a polyurethane resin having a crosslinked structure, wherein the polyurethane resin is a cured resin.
  • 0.01 to 5.0 parts by weight of a polyurethane resin having a crosslinked structure is added to 100 parts by mass of the aromatic polycarbonate resin, and the aromatic polycarbonate resin and the polyurethane resin having a crosslinked structure are mixed.
  • a method for producing a resin composition is provided.
  • the present technology provides a resin molded body obtained by molding the resin composition according to the present technology.
  • a resin composition in which surface properties such as fluidity, solvent resistance, chemical resistance, and scratch resistance are improved without reducing mechanical properties such as impact resistance.
  • a flame retardant for example, organic sulfonic acid, an organic sulfonic acid metal salt compound, etc.
  • the resin composition which provided the flame retardance further is provided.
  • this technique may use an aromatic polycarbonate resin containing a recovered polycarbonate resin such as a waste optical disk, the recovered polycarbonate resin such as a waste optical disk can be effectively used as a raw material. Can contribute to resource saving.
  • the resin composition of the first embodiment according to the present technology includes 100 parts by mass of an aromatic polycarbonate resin and 0.01 to 5.0 parts by mass of a polyurethane resin having a crosslinked structure, and the polyurethane resin is a cured resin.
  • the polyurethane resin having a crosslinked structure may be a photocurable resin obtained by curing a curable polyurethane resin composition with light (for example, ultraviolet light) or a thermosetting resin cured with heat.
  • the improvement in fluidity improves the processability (moldability, etc.) of the resin composition.
  • the content of the polyurethane resin having a crosslinked structure in the resin composition is 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. From the viewpoint of further improving the mechanical properties. 0.05 to 3.0 parts by mass is preferable.
  • the resin composition of the first embodiment according to the present technology includes an aromatic polycarbonate resin.
  • the content of the aromatic polycarbonate resin may be any amount, but is preferably 94.5 to 99.5% by mass, and preferably 96 to 98% by mass with respect to the total mass of the resin composition. More preferred.
  • the aromatic polycarbonate resin is used as a raw material for producing a molded part of the resin composition of the first embodiment according to the present technology, and is used for applications such as optical discs and housing materials for home appliances.
  • an aromatic polycarbonate resin produced by a reaction between a dihydric phenol and a carbonate precursor can be used.
  • the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.
  • the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.
  • the aromatic polycarbonate resin may be a polyester carbonate copolymerized with an aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or a derivative thereof within a range that does not impair the gist of the present technology.
  • an aromatic dicarboxylic acid for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or a derivative thereof within a range that does not impair the gist of the present technology.
  • other thermoplastic resins other than an aromatic polycarbonate resin can be mix
  • the amount of other thermoplastic resin blended varies depending on the type and purpose, but is usually preferably 1 to 30 parts by weight and more preferably 2 to 20 parts by weight per 100 parts by weight of the aromatic polycarbonate resin.
  • thermoplastic resins include, for example, general-purpose plastics represented by polyethylene resin, polypropylene resin, polyalkyl methacrylate resin, polyphenylene ether resin, polyacetal resin, polyamide resin, cyclic polyolefin resin, polyarylate resin (non-crystalline) And so-called super engineering plastics such as engineering plastics typified by polyarylate and liquid crystalline polyarylate), polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, and polyphenylene sulfide. .
  • thermoplastic elastomers such as olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers can also be used.
  • the aromatic polycarbonate resin contained in the resin composition of the first embodiment according to the present technology may include an aromatic polycarbonate resin having a branched structure (sometimes referred to as a branched aromatic polycarbonate resin).
  • the branched aromatic polycarbonate (PC) resin is not particularly limited as long as it is a branched aromatic polycarbonate resin.
  • PC branched aromatic polycarbonate resin
  • it has a branched nucleus structure derived from a branching agent represented by the following general formula (I).
  • the viscosity average molecular weight is 15,000 to 40,000, preferably 17,000 to 30,000, more preferably 17,000 to 27,000, and the amount of branching agent used is
  • the branched aromatic polycarbonate resin is preferably in the range of 0.01 to 3 mol%, more preferably 0.1 to 2.0 mol% with respect to the dihydric phenol compound.
  • R is hydrogen or an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or an n-pentyl group.
  • R1 to R6 are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, etc.) or a halogen atom (for example, chlorine Atoms, bromine atoms, fluorine atoms, etc.).
  • the branching agent represented by the general formula (I) is more specifically 1,1,1-tris (4-hydroxyphenyl) -methane; 1,1,1-tris (4-hydroxyphenyl) -ethane; 1,1,1-tris (4-hydroxyphenyl) -propane; 1,1,1-tris (2-methyl-4-hydroxyphenyl) -methane; 1,1,1-tris (2-methyl-4- 1,1,1-tris (3-methyl-4-hydroxyphenyl) -methane; 1,1,1-tris (3-methyl-4-hydroxyphenyl) -ethane; 1-tris (3,5-dimethyl-4-hydroxyphenyl) -methane; 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) -ethane; 1,1,1-tris (3- Chloro-4-hydroxy Phenyl) -methane; 1,1,1-tris (3-chloro-4-hydroxyphenyl) ethane; 1,1,1-tris (3,
  • branching agents may be used alone or in combination of two or more.
  • 1,1,1-tris (4-hydroxyphenyl) ethane is used as the branching agent
  • the amount used is 0.2 to 2.0 mol% with respect to the dihydric phenol compound.
  • it is 0.3 to 2.0 mol%, more preferably 0.4 to 1.9 mol%.
  • the amount is 0.2 mol% or more, the degree of freedom of blending is widened, and when the amount is 2.0 mol% or less, gelation is difficult during polymerization, and the production of an aromatic polycarbonate resin is easy.
  • the branched aromatic polycarbonate resin has a branched nucleus structure derived from the branching agent represented by the general formula (I), and is specifically represented by the following formula.
  • a, b and c are integers, and PC represents a polycarbonate portion.
  • PC represents a repeating unit represented by the following formula, for example, when bisphenol A is used as a raw material component.
  • the amount (ratio) of the branched aromatic polycarbonate resin in 100 parts by mass of the aromatic polycarbonate resin is preferably 10 to 100 parts by mass, and more preferably 50 to 100 parts by mass. If the amount of the branched aromatic polycarbonate resin is not 10 parts by mass or more, for example, a thin flame retardant effect may not be obtained.
  • the aromatic polycarbonate resin may include an unbranched polycarbonate resin that does not contain halogen in the molecular structure.
  • the unbranched polycarbonate resin is preferably a polymer having a structural unit represented by the following formula (II).
  • X represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, etc.) And when X is plural, they may be the same or different, and a and b are each an integer of 1 to 4.
  • Y represents a single bond, an alkylene group having 1 to 8 carbon atoms or an alkylidene group having 2 to 8 carbon atoms (for example, methylene group, ethylene group, propylene group, butylene group, penterylene group, hexylene group, ethylidene group, isopropylene group).
  • a cycloalkylene group having 5 to 15 carbon atoms or a cycloalkylidene group having 5 to 15 carbon atoms for example, a cyclopentylene group, a cyclohexylene group, a cyclopentylidene group, a cyclohexylidene group, etc.
  • X is preferably a hydrogen atom
  • Y is preferably an ethylene group or a propylene group.
  • This aromatic polycarbonate resin can be easily produced by reacting a dihydric phenol represented by the following formula (IV) with phosgene or a carbonic acid diester compound. That is, for example, in a solvent such as methylene chloride, in the presence of a known acid acceptor or viscosity average molecular weight regulator, by reaction of a dihydric phenol with a carbonate precursor such as phosgene, or dihydric phenol and diphenyl carbonate. Is produced by a transesterification reaction with a carbonate precursor.
  • dihydric phenols represented by the formula (IV).
  • dihydric phenols other than the dihydric phenols represented by the formula (IV) include dihydroxybenzenes such as hydroquinone, resorcinol and methylhydroquinone, 1,5-dihydroxynaphthalene; and dihydroxynaphthalene such as 2,6-dihydroxynaphthalene. And the like. These dihydric phenols may be used alone or in combination of two or more.
  • the carbonic acid diester compound include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.
  • polymerization of a polycarbonate may be used, and various things can be used.
  • the monohydric phenol include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, and nonylphenol.
  • the aromatic polycarbonate used in the present invention may be a mixture of two or more aromatic polycarbonates.
  • the aromatic polycarbonate preferably has a viscosity average molecular weight of 10,000 to 100,000, particularly preferably 20,000 to 40,000, from the viewpoint of mechanical strength and moldability. .
  • the aromatic polycarbonate resin contained in the transmissive resin composition of the first embodiment according to the present technology may include an aromatic polycarbonate-polyorganosiloxane copolymer.
  • the aromatic polycarbonate-polyorganosiloxane copolymer comprises an aromatic polycarbonate part and a polyorganosiloxane part, and includes an aromatic polycarbonate structural unit represented by the following general formula (V) and a polysiloxane represented by the general formula (VI). It contains an organosiloxane structural unit.
  • R 5 and R 6 each represent a halogen atom, an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) or an optionally substituted phenyl group, and R When there are a plurality of 5 and R 6 , they may be the same or different.
  • Y is a single bond, an alkylene group or alkylidene group having 1 to 20 carbon atoms (preferably 2 to 10 carbon atoms), a cycloalkylene group or cycloalkylidene group having 5 to 20 carbon atoms (preferably 5 to 12 carbon atoms),- O—, —S—, —SO—, —SO 2 — or —CO— is shown, and an isopropylidene group is preferred.
  • p and q are each an integer of 0 to 4 (preferably 0), and when there are a plurality of p and q, they may be the same or different.
  • m represents an integer of 1 to 100 (preferably an integer of 5 to 90). When m is from 1 to 100, an appropriate viscosity average molecular weight can be obtained in the aromatic polycarbonate-polyorganosiloxane copolymer.
  • R 7 to R 10 each represents an alkyl group having 1 to 6 carbon atoms or a phenyl group which may have a substituent, and they may be the same or different.
  • Specific examples of R 7 to R 10 include methyl groups, ethyl groups, propyl groups, n-butyl groups, isobutyl groups, amyl groups, isoamyl groups, hexyl groups and other alkyl groups, phenyl groups, tolyl groups, xylyl groups, and the like. Mention may be made of phenyl aryls such as naphthyl groups.
  • R 11 represents an aliphatic or aromatic organic residue, and is preferably a divalent organic compound residue such as an o-allylphenol residue, a p-hydroxystyrene residue, and an eugenol residue.
  • the method for producing the aromatic polycarbonate-polyorganosiloxane copolymer includes, for example, using an aromatic polycarbonate oligomer and a polyorganosiloxane having a reactive group at the end constituting the polyorganosiloxane part in a solvent such as methylene chloride. It can be produced by dissolving and adding a dihydric phenol such as bisphenol A using a catalyst such as triethylamine and interfacial polycondensation reaction.
  • This aromatic polycarbonate-polyorganosiloxane copolymer is, for example, disclosed in JP-A-3-292359, JP-A-4-202465, JP-A-8-81620, JP-A-8-302178, and JP-A-10-302. -7897 and the like.
  • the degree of polymerization of the aromatic polycarbonate structural unit of the aromatic polycarbonate-polyorganosiloxane copolymer is preferably 3 to 100, and the degree of polymerization of the polyorganosiloxane structural unit is preferably about 2 to 500, more preferably about 2 to 300. More preferably, about 2 to 140 is used.
  • the polyorganosiloxane content of the aromatic polycarbonate-polyorganosiloxane copolymer is usually about 0.1 to 10% by mass, preferably 0.3 to 6% by mass.
  • the viscosity-average molecular weight of the aromatic polycarbonate-polyorganosiloxane copolymer used in the transmission resin composition of the first embodiment according to the present technology is usually about 5,000 to 100,000, preferably 10,000 to 30,000, particularly preferably 12,000 to 30,000.
  • these viscosity average molecular weights (Mv) can be obtained in the same manner as the above polycarbonate resin.
  • the aromatic polycarbonate resin shown above may be a newly manufactured virgin material, waste material, end material, sprue material, waste, etc. generated in the manufacturing process, or a product (for example, a digital versatile disc (DVD), It may be a recovered material or a waste material of an optical disc (substrate) such as a compact disc (CD), MO, MD, or Blu-ray disc (BD) (recycled polycarbonate resin).
  • the recycled polycarbonate resin is preferably a recycled polycarbonate resin recovered from the market.
  • the aromatic polycarbonate resin may contain a recycled polycarbonate resin or may be composed of a recycled polycarbonate resin.
  • the content of the recycled polycarbonate resin is preferably 1 to less than 100% by mass with respect to the total mass of the aromatic polycarbonate resin.
  • the recovered optical disc there are various deposits such as a metal reflection layer, a plating layer, a recording material layer, an adhesive layer, a label, etc., but in the present invention, these may be used as provided.
  • Such impurities and sub-materials may be used after being separated and removed by a conventionally known method.
  • a metal reflection layer such as Al, Au, Ag, Si, an organic dye containing a cyanine dye, Te, Se, S, Ge, In, Sb, Fe, Tb, Co, Ag, Ce, Bi, etc.
  • Recording material layers acrylic acrylates, ether acrylates, vinyl monomers and oligomers, adhesive layers comprising at least one polymer, UV curable monomers, oligomers, at least one polymer and polymerization initiators and pigments, Examples include label ink layers in which an auxiliary agent is mixed, but are not limited thereto, and may include a film forming material and a coating material that are usually used in an optical disk.
  • an optical disk can be finely crushed and used as a PC resin raw material as it is, or kneaded and melted with a predetermined additive and pelletized.
  • the recovery disk may be directly put into a hopper or the like of the injection molding machine together with various additives described later to obtain a molded body made of the resin composition.
  • deposits such as a metal reflection layer, a recording material layer, an adhesive layer, a surface hardened layer, and a label are, for example, It can be removed by a mechanical or chemical method proposed in JP-A-6-223416, JP-A-10-269634, JP-A-10-249315, or the like.
  • the weight average molecular weight of the aromatic polycarbonate resin can be measured in terms of polystyrene based on a polystyrene molecular weight standard substance (sample) by GPC (Gel Permeation Chromatography) measurement using a chloroform solvent.
  • the molecular weight of the aromatic polycarbonate resin may be any value, but the molecular weight is preferably 36000 to 63,000 in terms of weight average molecular weight (polystyrene conversion). The reason is that if the weight average molecular weight of the aromatic polycarbonate resin is larger than 63,000, the flowability (workability) at the time of melting of the resin composition as the final target product tends to be deteriorated. On the other hand, when it is smaller than 36000, the solvent resistance tends to decrease and solvent cracks (cracks due to chemicals) tend to occur, and the impact resistance tends to decrease.
  • the aromatic polycarbonate resin contained in the resin composition preferably has a weight average molecular weight of 40,000 to 59,000, and more preferably 44,000 to 54,000, from the viewpoint of mechanical strength and moldability.
  • the resin composition according to the first embodiment of the present technology includes 0.01 to 5.0 parts by mass of a cured polyurethane resin having a crosslinked structure with respect to 100 parts by mass of the aromatic polycarbonate resin. Below, the polyurethane resin which has a crosslinked structure is demonstrated in detail.
  • the polyurethane resin is not particularly limited as long as the polyurethane resin is a cured resin polyurethane resin having a crosslinked structure, but it has excellent surface physical properties such as chemical resistance.
  • a polyurethane resin having a cross-linked structure in which a polyester polyol and polyisocyanate are reacted to cross-link three-dimensionally is preferable.
  • the mass ratio of the polyester polyol to be reacted and the polyisocyanate may be any ratio, but is preferably 100: 50 to 100: 200.
  • a polyurethane resin contains the structural unit derived from a polyester polyol and the structural unit derived from polyisocyanate.
  • the polyurethane resin having a crosslinked structure can be obtained, for example, by mixing two liquids of a polyester polyol and a polyisocyanate, and then producing by a thermosetting reaction. Using a pellet-like aromatic polycarbonate resin, two liquids of polyester polyol and polyisocyanate are mixed and heated in the range of 60 to 200 ° C. for several seconds to 10 minutes. To form a polyurethane resin coating. Thereafter, for example, by kneading with a twin-screw extruder, the resin composition of the first embodiment according to the present technology including an aromatic polycarbonate resin and a polyurethane having a crosslinked structure can be produced.
  • the present technology can also be obtained by applying a polyurethane resin-coated resin composition by heating after applying two liquids of polyester polyol and polyisocyanate on a color plate made of an aromatic polycarbonate resin and re-pelletizing.
  • the resin composition of 1st Embodiment which concerns on can be manufactured.
  • a coated product obtained by coating a polyurethane resin on a carbonate resin is not particularly limited, and may be a conventionally known method.
  • a method may be used in which a polyurethane resin is applied to a carbonate resin (for example, aromatic carbonate resin) substrate, and then the obtained two-layer film is baked at the same time.
  • the method for coating may be appropriately selected from conventionally known methods in consideration of the form of the polyurethane resin to be used and the surface shape of the base material of the carbonate resin (for example, aromatic carbonate resin), and is particularly limited.
  • it can be applied by air spray, airless spray, shower, carte coater, bell, or other ordinary electrostatic coating.
  • the obtained coated product may be subjected to natural drying or forced drying (for example, hot air drying, near infrared drying, electromagnetic wave drying, etc.).
  • the method for baking is not particularly limited, but the baking temperature is 70 to 110 ° C. in consideration of the possibility that the baking may cause deterioration of the base material of the carbonate resin (for example, aromatic carbonate resin).
  • the baking time at that time depends on the baking temperature and may be appropriately set in consideration of energy efficiency, but it is 10 to 60 minutes. It is preferable to set it for 15 to 40 minutes.
  • the average particle diameter of the polyurethane resin powder having a crosslinked structure may be any average particle diameter, but is preferably 0.5 mm to 1.5 mm.
  • the average particle size of the polyurethane resin having a crosslinked structure is 0.5 mm to 1.5 mm, the dispersibility and mixing properties of the polyurethane resin are improved in the aromatic polycarbonate resin.
  • the surface properties (chemical resistance, etc.) and fluidity will be further improved while the mechanical properties of the resin composition are better maintained.
  • the ratio of the particle size of the polyurethane resin powder to 0.5 mm to 1.5 mm may be any ratio to the total polyurethane resin powder, but is 70% or more. It is preferable.
  • the content is 70% or more, the dispersibility and mixing properties of the polyurethane resin become better in the aromatic polycarbonate resin.
  • the surface properties (chemical resistance, etc.) and fluidity will be further improved while the mechanical properties of the resin composition are better maintained.
  • the particle size distribution of the polyurethane resin powder can be measured as follows.
  • low tap measurement was used.
  • the low-tap method is a method for sorting by sieve eyes, and is a measurement method for measuring the mass of a sample remaining on each sieve and describing the cumulative distribution on a graph to obtain an average particle size distribution.
  • the particle size of the polyurethane resin powder having a crosslinked structure can be changed by adjusting the pulverization conditions.
  • a polyurethane resin having a particle size of 0.5 mm to 1.5 mm and a ratio of 70% or more with respect to the total powder of the polyurethane resin can be produced by pulverizing the polyurethane resin by a freeze pulverization method.
  • the ratio of the polyester polyol and the polyisocyanate is such that the ratio of the number of hydroxyl equivalents in the polyester polyol to the number of isocyanate equivalents in the polyisocyanate (number of hydroxyl equivalents in the polyester polyol component: number of isocyanate equivalents in the polyisocyanate) is 100: 50 to 100. Is preferably set to be in the range of 200, more preferably in the range of 100: 80 to 100: 180. When the number of hydroxyl group equivalents in the polyester polyol is 100 and the number of equivalents of isocyanate in the polyisocyanate is less than 50, the crosslinking reaction between the polyester polyol and the polyisocyanate becomes slightly insufficient, and the coating speed is reduced.
  • the curability is slightly lowered and the physical properties of the coating film such as abrasion resistance, hardness, weather resistance, water resistance, solvent resistance, chemical resistance and the like are slightly lowered.
  • the number of equivalents of hydroxyl group in the polyester polyol is set to 100 and the number of equivalents of isocyanate in the polyisocyanate exceeds 200, the physical properties may be slightly lowered due to the presence of excess polyisocyanate.
  • the curable polyurethane resin composition may appropriately contain a solvent for dissolving or dispersing the polyester polyol and / or polyisocyanate.
  • the solvent may be contained in one or both of the polyester polyol and polyisocyanate.
  • a solvent can also be used in order to dilute so that it may become a suitable viscosity.
  • the solvent examples include hydrocarbon solvents such as toluene, xylene, solvent naphtha, methylcyclohexane, and ethylcyclohexane; ester solvents such as ethyl acetate, butyl acetate, and ethylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, And ketone solvents such as diisobutyl ketone.
  • hydrocarbon solvents such as toluene, xylene, solvent naphtha, methylcyclohexane, and ethylcyclohexane
  • ester solvents such as ethyl acetate, butyl acetate, and ethylene glycol monomethyl ether
  • acetone methyl ethyl ketone
  • methyl isobutyl ketone methyl isobutyl ketone
  • ketone solvents such as diisobut
  • the curable polyurethane resin composition may be a natural dye, an organic synthetic dye, a pigment, an inorganic pigment, or a bright material (a flake pigment that imparts a glittery feeling or light interference to the coating film).
  • a coloring component such as can be contained. These coloring components may be contained in either polyester polyol or polyisocyanate, but are preferably contained in polyester polyol. Only 1 type may be sufficient as a coloring component, and 2 or more types may be sufficient as it. Needless to say, the polyurethane resin having a crosslinked structure may be a clear coating containing no coloring component.
  • natural pigments include carotenoid pigments such as carotene, carotenal, capsanthin, lycopene, bixin, crocin, canthaxanthin and anato; anthocyanidins such as shisonin, raphanin and enocyanin, chalcones such as safrole yellow and safflower, Flavonols such as rutin and quercetin, flavonoids such as flavones such as cacao pigments, flavin pigments such as riboflavin; anthraquinones such as lacaic acid, carminic acid (cochineal), kermesic acid, alizarin, shikonin Quinone dyes such as naphthoquinones such as alkanin and echinochrome; polyphyrin dyes such as chlorophyll and hemoglobin; diketone dyes such as curcumin (turmeric); Tashianijin based dyes; and the like.
  • organic synthetic dyes or pigments include those defined by Ordinance No. 30 of the Ministry of Health and Welfare.
  • Red 202 (Risor Rubin BCA), Red 203 (Rake Red C), Red 204 (Rake Red CBA), Red 205 (Risor Red), Red 206 (Risor Red CA), Red 207 (Risole) Red BA), Red 208 (Risor Red SR), Red 219 (Brilliant Lake Red R), Red 220 (Deep Maroon), Red 221 (Toluidine Red), Red 228 (Parmaton Red), orange No. 203 (Permanent Orange), Orange No. 204 (Bench Gin Orange G), Yellow 205 (Bench Gin Yellow G), Red No. 404 (Brilliant Fast Scarlet), Red No. 405 (Permanent Red F5R), Orange No. 401 ( Hansa Orange), Yellow No. 401 ( Nzaero), Blue No. 404 (phthalocyanine blue), and the like.
  • inorganic pigments include silicic anhydride, magnesium silicate, talc, kaolin, bentonite, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, light calcium carbonate, heavy calcium carbonate, light magnesium carbonate, and heavy magnesium carbonate.
  • the bright material include flaky aluminum, vapor-deposited aluminum, aluminum oxide, oxybismuth chloride, mica, titanium oxide-coated mica, iron oxide-coated mica, mica-like iron oxide, titanium oxide-coated silica, and titanium oxide-coated alumina.
  • Examples thereof include iron oxide-coated silica, iron oxide-coated alumina, glass flakes, colored glass flakes, vapor-deposited glass flakes, and hologram films.
  • the size of these glitter materials is not particularly limited, but is preferably 1-30 ⁇ m in the longitudinal direction and 0.001-1 ⁇ m in thickness.
  • the curable polyurethane resin composition may contain other natural product-derived resins as necessary.
  • other natural product-derived resins may be contained in either polyester polyol or polyisocyanate, but are preferably contained in polyester polyol.
  • One type of other natural product-derived resins may be used, or two or more types may be used.
  • natural product-derived resins are not particularly limited, but include, for example, plant fibers, cellulose resins, polyhydroxycarboxylic acids typified by polylactic acid, polycaprolactam, modified polyvinyl alcohol, and the like, as well as typified by polycaprolactone. Examples include biodegradable aliphatic polyester. As other natural product-derived resins, those that are soluble in the above-mentioned solvents are particularly preferable, and cellulose-derived resins are particularly preferable. For example, physical properties such as surface hardness of the obtained cured coating film can be further improved by containing a small amount of one or more selected from cellulose, nitrocellulose, and cellulose acetate butyrate.
  • Examples of other commercially available products that can be used as other natural product-derived resins include nitrocellulose, industrial nitrified cotton “BNC-HIG-2” manufactured by Bergerac NC, France, and industrial nitrified cotton manufactured by Korea CNC.
  • RS1-4 “Swancell HM1-4” manufactured by Kyosei Yoko Co., Ltd., “Selnova BTH1-4” manufactured by Asahi Kasei Chemicals Co., Ltd.), etc.
  • a conventionally known surface conditioner wax, repellency inhibitor, antifoaming agent, etc.
  • plasticizer plasticizer
  • UV stabilizer antioxidant
  • fluidity modifier e.g., ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol dimethoxysulfate, etc.
  • additives such as an anti-sagging agent, a matting agent, a polishing agent, and an antiseptic can be appropriately contained.
  • additives may be contained in either polyester polyol or polyisocyanate, but are preferably contained in polyester polyol.
  • the polyurethane resin having a crosslinked structure is a cured product obtained by curing a curable polyurethane resin composition containing at least a polyester polyol and a polyisocyanate, and is a resin obtained by curing a polyester polyol with a polyisocyanate.
  • the polyurethane resin having a crosslinked structure can be obtained, for example, by mixing polyester polyol and polyisocyanate as described above.
  • the resin composition of 1st Embodiment which concerns on this technique can be obtained by adding the polyurethane resin which has the obtained crosslinked structure to polycarbonate resin (dry blending), and kneading
  • polyester polyol as a raw material for the polyurethane resin having a crosslinked structure will be described.
  • the hydroxyl value of the polyester polyol may have any value, but is preferably 30 to 300.
  • the resulting polyurethane resin may have a slightly lower crosslink density.
  • the chemical resistance and resistance of the resin composition added and kneaded to the aromatic polycarbonate resin may be reduced. Abrasion, weather resistance, water resistance, and solvent resistance may be slightly insufficient.
  • the hydroxyl value of the polyester polyol exceeds 300, on the contrary, since the crosslinking is slightly advanced, the compatibility with the aromatic polycarbonate resin is slightly deteriorated, and the mechanical properties and chemical resistance are slightly decreased. There is.
  • the hydroxyl value can be obtained by measurement by the method described in JIS K-1557-1.
  • the weight average molecular weight of the polyester polyol may have any value, but is preferably 10,000 to 500,000. If the weight average molecular weight of the polyester polyol is less than 10,000, a polyurethane structure having a crosslinked structure is formed, and the chemical resistance of the resin composition added to and kneaded with the polycarbonate resin may be slightly insufficient. . On the other hand, when the weight average molecular weight of the polyester polyol exceeds 500,000, the viscosity becomes high, and when added to the polycarbonate resin and kneaded, the dispersibility tends to be slightly deteriorated, leading to a decrease in physical properties.
  • Polyester polyol can be produced by, for example, a method of reacting a low molecular weight polyol and a polycarboxylic acid, a method of ring-opening polymerization reaction of a cyclic ester compound such as ⁇ -caprolactone, and the like.
  • low molecular weight polyol examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neo Pentyl glycol, 1,8-octanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300 to 6000), dipropylene glycol, tripropylene glycol Bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, hydroquinone and their alkylene oxide adducts be able to.
  • polycarboxylic acid examples include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid.
  • Isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acids, and anhydrides or ester-forming derivatives thereof can be used.
  • the polyester polyol may be a polyester polyol obtained using a vegetable oil-derived raw material.
  • the vegetable oil-derived raw material is preferably at least one selected from the group consisting of vegetable oil or fatty acids thereof, carboxylic acids produced using vegetable oil as a raw material, and raw materials having a hydroxyl group derived from vegetable oil.
  • vegetable oil or vegetable oil fatty acid include Chinese tung oil (fatty acid), linseed oil (fatty acid), dehydrated castor oil (fatty acid), tall oil fatty acid, cottonseed oil (fatty acid), soybean oil (fatty acid), olive oil (fatty acid), safflower oil (Fatty acid), castor oil (fatty acid) rice bran oil (fatty acid), hydrogenated coconut oil (fatty acid), coconut oil (fatty acid), palm oil (fatty acid) and the like.
  • carboxylic acids produced from vegetable oils include, for example, 12-hydroxystearic acid, heptyl acid, undecylenic acid, sebacic acid produced from castor oil; rosin purified from pine ani, and hydrogenated rosin that is a hydride thereof.
  • dimer acid produced from a dry vegetable oil fatty acid such as polymerized rosin tall oil fatty acid which is a polymer thereof, and hydrogenated dimer acid which is a hydride thereof; isostearic acid produced as a by-product during dimer acid production, and the like.
  • Examples of the raw material having a hydroxyl group derived from vegetable oil include heptanal, octanol, 1,10-decanediol produced from castor oil; glycerin purified from each vegetable oil; and the like.
  • the polyester polyol may be obtained using the above-described vegetable oil-derived raw material, and its production method is not particularly limited. For example, it is generally used for the above-mentioned vegetable oil-derived raw material and, if necessary, the esterification reaction.
  • the acid component and / or alcohol component to be obtained can be obtained by an esterification reaction.
  • Examples of the acid component that can be used in obtaining the polyester polyol include benzoic acid, p-tert-butylbenzoic acid, isophthalic acid, phthalic anhydride, terephthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, and azelain.
  • Acid sebacic acid, isosebacic acid, oxalic acid, trimellitic acid, (anhydrous) succinic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, dodecanoic acid, tetrahydro (anhydrous) phthalic acid, hexahydro (anhydrous) Phthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, tetrachloro (anhydride) phthalic acid, hexachloro (anhydride) phthalic acid, tetrabromo (anhydride) phthalic acid, glutaric acid, adipic acid, pimelic acid, uberic acid, hydrogenated phthalate Acid, 1,4-cyclohexanedicarboxylic acid, etc. And the like. In addition, only 1 type may be sufficient as an acid component, and 2 or more types may be sufficient as it.
  • Examples of the alcohol component that can be used for obtaining the polyester polyol include ethylene glycol, neopentyl glycol, diethylene glycol, tetramethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and 2,3,4-trimethyl-1 , 3-pentanediol, 3-methylpentene-1,5-diol, 1,4-cyclohexanedimethanol, ethylene oxide or propylenoxide of bisphenol A or hydrogenated bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene Glycol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-ethyl-1,3-propanediol, trisic Divalent alcohol components such as decanedimethanol, cyclohexanedicarboxylic acid, cyclohexanedimethanol, cyclohexaned
  • the amount of the vegetable oil-derived raw material used is preferably set so as to be 30 to 100% by mass, although the content of the vegetable oil-derived raw material in the obtained polyester polyol may be optional.
  • the content ratio of the vegetable oil-derived raw material in the polyester polyol is less than 30% by mass, the effect of preventing global warming obtained by using a carbon neutral material tends to be slightly reduced.
  • what is necessary is just to employ
  • the polyisocyanate has at least one isocyanate group and preferably has two or more isocyanate groups.
  • polyisocyanate examples include aromatic polyisocyanates, aliphatic polyisocyanates, cycloaliphatic polyisocyanates, alicyclic polyisocyanates, or reaction products of these polyisocyanates and polyols.
  • tolylene diisocyanate TDI
  • diphenylmethane diisocyanate MDI
  • polyphenylmethane polyisocyanate CAde MDI
  • modified MDI modified diphenylmethane diisocyanate
  • XDI xylylene diisocyanate
  • HMDI hexamethylene diisocyanate
  • Aromatic polyisocyanates or trimer compounds of these polyisocyanates, reaction products of these polyisocyanates and polyols, and the like are preferable.
  • the polyisocyanate only one type of polyisocyanate may be used, or two or more types of polyisocyanate may be used.
  • Organic sulfonic acid and organic sulfonic acid metal salt compound In the resin composition of the first embodiment according to the present technology, the organic sulfonic acid and / or the organic sulfonic acid metal salt compound is further added in an amount of 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. May be included.
  • the organic sulfonic acid and the organic sulfonic acid metal salt compound will be described in detail.
  • the organic sulfonic acid is not particularly limited, but is preferably an aromatic organic sulfonic acid.
  • the organic sulfonic acid metal salt compound is not particularly limited, but is preferably an aromatic sulfonic acid metal salt compound.
  • the aromatic sulfonic acid metal salt compound contains a sulfonic acid metal base, and the content of the sulfonic acid metal base may be arbitrarily adjusted and may be any amount, but is preferably 0.1 to 10 mol%.
  • examples of the low molecular weight compound include perfluoroalkanesulfonic acid, alkylbenzene sulfonic acid, halogenated alkylbenzene sulfonic acid, alkyl sulfonic acid, naphthalene sulfonic acid and the like, or alkali metals thereof.
  • examples of the salt or the alkaline earth metal salt and the high molecular weight compound include, for example, a polymer having an aromatic ring and a predetermined amount of sulfonic acid and / or a metal salt thereof described in Patent 4196862 and Patent 4196661. Are listed.
  • polystyrene (PS) sulfonic acid or polystyrene (PS) sulfonic acid metal salt examples include polystyrene (PS) sulfonic acid or polystyrene (PS) sulfonic acid metal salt, high impact polystyrene (HIPS) sulfonic acid or high impact polystyrene (HIPS) sulfonic acid metal salt, or sulfonic acid.
  • HIPS high impact polystyrene
  • HIPS high impact polystyrene
  • AS Styrene / acrylonitrile copolymer resin
  • organic sulfonic acid or organic sulfonic acid metal salt compounds ranging from low molecular weight to high molecular weight, but in general, dispersion when high molecular weight is kneaded into aromatic polycarbonate resin It is preferable because of its good properties and excellent storage stability under high temperature and high humidity conditions.
  • an alkali metal salt or alkaline earth metal salt thereof specifically, for example, polystyrene sulfonic acid or potassium thereof.
  • salt One or more selected from these may be mixed and used at an appropriate ratio, but when using polystyrene sulfonic acid or its potassium salt, a high flame retardant effect can be obtained with a very small amount of addition, preferable.
  • those weight average molecular weights are 30000 or more, and when it is 40000 or more and 300000 or less, since the balance of solvent resistance and compatibility is further maintained, it is more preferable.
  • the content of the organic sulfonic acid or the organic sulfonic acid metal salt compound is 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin.
  • the flame retardant effect is further enhanced, and in the case of 0.05 to 1 mass part, a stronger flame retardant effect can be obtained. If it is less than 0.05 parts by mass, it may be difficult to obtain a flame retardant effect. If it exceeds 1.5 parts by mass, the compatibility with the aromatic polycarbonate resin may be reduced, and negative flame retardant.
  • the flame retardant level may be lower than the effect, that is, the case of not containing.
  • the resin composition of the first embodiment according to the present technology may further include an anti-drip agent.
  • the content of the anti-drip agent may be 0.8 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin.
  • an anti-drip agent is included. The drip phenomenon during combustion can be suppressed.
  • the anti-drip agent include a fluoroolefin resin.
  • fluoroolefin resin capable of suppressing the drip phenomenon
  • examples of the fluoroolefin resin capable of suppressing the drip phenomenon include a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a copolymer with a tetrafluoroethylene-ethylene monomer. Any one of them or a mixture of two or more of them can be used.
  • fluoroolefin resins it is particularly preferable to use a tetrafluoroethylene polymer or the like, and the average molecular weight is 50,000 or more, and preferably in the range of 100,000 to 20,000,000.
  • fluoroolefin resin what has fibril formation ability is more preferable.
  • the content of the anti-drip agent such as fluoroolefin resin may be 0.8 parts by mass or less, preferably in the range of 0.001 to 0.8 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin.
  • the range of 0.01 to 0.5 parts by mass is more preferable, and the range of 0.05 to 0.3 parts by mass is even more preferable.
  • the content of the anti-drip agent such as fluoroolefin resin is less than 0.001 part by mass with respect to 100 parts by mass of the aromatic polycarbonate resin, it may be difficult to suppress the drip phenomenon.
  • the content of the anti-drip agent such as fluoroolefin resin is more than 0.8 parts by mass, the molded product may be slightly whitened and transparency may be slightly impaired.
  • the resin composition of the first embodiment according to the present technology includes, as other components (other additives), for example, an antioxidant (hindered phenol-based, phosphorus-based, sulfur-based), antistatic Agent, UV absorber (benzophenone, benzotriazole, hydroxyphenyltriazine, cyclic imino ester, cyanoacrylate), light stabilizer, plasticizer, compatibilizer, colorant (pigment, dye), light stability Agents, crystal nucleating agents, antibacterial agents, flow modifiers, infrared absorbers, phosphors, hydrolysis inhibitors, mold release agents, silicone flame retardants or surface treatment agents may be contained.
  • an antioxidant hinderephthalate, hydroxyphenyltriazine, cyclic imino ester, cyanoacrylate
  • light stabilizer plasticizer
  • compatibilizer colorant (pigment, dye)
  • colorant pigment
  • light stability Agents crystal nucleating agents, antibacterial agents, flow modifiers, infrared absorbers, phosphors, hydrolysis inhibitors,
  • the silicone compound is used to impart flame retardancy to the resin composition of the first embodiment according to the present technology.
  • the addition amount of the silicone-based flame retardant in the resin composition is preferably 0.001 to 0.02 (0.1 to 2% by mass) as a mass ratio with respect to the resin composition.
  • the addition amount of the silicone-based flame retardant is less than 0.001 (0.1% by mass) in terms of mass ratio with respect to the resin composition, the effect of imparting flame retardancy to the resin composition may not be sufficient.
  • the addition amount is more than 0.02 (2% by mass)
  • the economy may be deteriorated due to the decrease in efficiency, and the effect of imparting flame retardancy may be saturated and the efficiency may be decreased.
  • Second Embodiment (Example of Manufacturing Method of Resin Composition)> [3-1. Method for producing resin composition]
  • the manufacturing method of the resin composition of 2nd Embodiment (example of a resin composition) which concerns on this technique is demonstrated in detail.
  • a polyurethane resin having a crosslinked structure is added to 100 parts by weight of an aromatic polycarbonate resin. It is a manufacturing method of the resin composition including adding and knead
  • the polyurethane resin having a crosslinked structure is preferably a curable resin, and may be a photocurable resin or a thermosetting resin.
  • the aromatic polycarbonate resin and the polyurethane resin having a cross-linked structure used in the method for producing the resin composition of the second embodiment according to the present technology are the first operations according to the present technology, except as described below.
  • the content of the aromatic polycarbonate resin and the polyurethane resin having a crosslinked structure contained in the resin composition in the form is the same as the aromatic polycarbonate resin and the crosslinked structure used in the method for producing the resin composition of the second embodiment according to the present technology. It can be applied as it is to the polyurethane resin it has.
  • the resin composition produced by the method for producing a resin composition of the second embodiment according to the present technology while maintaining the performance of mechanical properties such as impact resistance, fluidity, solvent resistance, Surface properties such as chemical resistance and scratch resistance can be improved.
  • the improvement in fluidity improves the processability of the resin composition.
  • the amount of the polyurethane resin having a crosslinked structure added to 100 parts by mass of the aromatic polycarbonate resin is 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. From the viewpoint of improvement, the amount is preferably 0.05 to 3.0 parts by mass.
  • the manufacturing method of the resin composition of 2nd Embodiment which concerns on this technique is as follows, for example.
  • First embodiment (example of resin composition)>
  • the organic sulfonic acid and / or organic sulfonic acid metal salt compound, the anti-drip agent, other components and / or the silicone compound are added in predetermined amounts. And mix. After mixing, for example, it is dispersed substantially uniformly with a Henschel mixer or a tumbler.
  • the resin composition is obtained by melt-kneading with a single screw or twin screw extruder and cutting the resulting strand with a pelletizer to produce pellets.
  • the resin composition manufactured by the manufacturing method of the resin composition of 2nd Embodiment which concerns on this technique is not restricted to what was processed into the pellet form, The state (powder state or fluid state) which mixed each component And those processed into a form different from the pellet (such as a sheet).
  • a method of adding a component of a polyurethane resin having a cross-linked structure of 0.01 to 5.0 parts by mass to a component of 100 parts by mass of an aromatic polycarbonate resin includes, for example, pellets of 100 parts by mass of an aromatic polycarbonate resin
  • a method of adding 0.01 to 5.0 parts by mass of a polyurethane resin component or the like so that a coating film is formed on the surface, 0.01% on a color plate made of 100 parts by mass of an aromatic polycarbonate resin An example is a method of adding a component of polyurethane resin of up to 5.0 parts by mass so as to coat it.
  • the method for producing the resin composition of the second embodiment according to the present technology includes producing a polyurethane resin having a crosslinked structure by reacting a polyester polyol and a polyisocyanate.
  • a method for producing a polyurethane resin having a crosslinked structure by reacting a polyester polyol and a polyisocyanate is, for example, mixing two liquids of a polyester polyol and a polyisocyanate, and then performing a thermosetting reaction or photocuring. This is a manufacturing method.
  • the resin molded body of the third embodiment according to the present technology is a resin molded body obtained by molding the resin composition of the first embodiment according to the present technology.
  • the resin molded body of the third embodiment according to the present technology may be a resin molded body including the resin composition of the first embodiment according to the present technology.
  • the resin composition of the first embodiment according to the present technology improves processability by improving fluidity without lowering mechanical properties, and further improves surface properties such as chemical resistance. It is possible to obtain a resin molded article suitable for equipment / copiers, in-vehicle use, and medical use.
  • the resin molded body of the third embodiment according to the present technology can be manufactured as follows, for example. Injection molding of pellets made of the resin composition of the first embodiment according to the present technology, or pellets made of the resin composition manufactured from the method for producing the resin composition of the second embodiment according to the present technology , Injection compression molding, extrusion molding, blow molding, vacuum molding, press molding, foam molding, or supercritical molding, etc. to a predetermined shape (for example, home appliances, automobiles, information equipment, office equipment, telephones, stationery, furniture) Or molded into housings or parts of various products such as fibers) to obtain a resin molded body.
  • a predetermined shape for example, home appliances, automobiles, information equipment, office equipment, telephones, stationery, furniture
  • molded into housings or parts of various products such as fibers to obtain a resin molded body.
  • the present technology is not limited to the above embodiments, and can be changed without departing from the gist of the present technology.
  • the present technology may have the following configurations.
  • [1] Including 100 parts by weight of an aromatic polycarbonate resin and 0.01 to 5.0 parts by weight of a polyurethane resin having a crosslinked structure, A resin composition, wherein the polyurethane resin is a cured resin.
  • the ratio of the particle size of the polyurethane resin powder having the crosslinked structure to 0.5 mm to 1.5 mm is 70% or more with respect to the total powder of the polyurethane resin having the crosslinked structure, [1] or The resin composition as described in [2].
  • Comparative Example 1-5 was a coated product, and was manufactured as follows. In Comparative Example 1-5 (coated product), the coating material was applied to the surface of the substrate by a roll coater method, a spray method, or a dipping method. After coating, a desired coating film was formed on the substrate surface by heating and drying at 60 to 120 ° C. for several seconds to 10 minutes as necessary.
  • the number of isocyanate equivalents of the polyester polyol (Placcel PCL305 (manufactured by Daicel Chemical Industries)) and the polyisocyanate curing agent (Duranate TPA-100 (manufactured by Asahi Kasei Kogyo)) is 100: 100.
  • a two-component curable coating composition was obtained.
  • compositions (parts by mass) of each component of the resin compositions of Examples 1-1 to 1-10 and the evaluation results of fluidity (g / 10 min), tensile strength (%), chemical resistance and bending strength are shown below. Table 1 shows. Further, the composition (parts by mass) of each component of the resin compositions of Comparative Examples 1-1 to 1-5, and evaluation results of fluidity (g / 10 min), tensile strength (%), chemical resistance, and bending strength Is shown in Table 2 below.
  • composition (parts by mass) of each component of the resin compositions of Examples 2-1 to 2-10, fluidity (g / 10 min), tensile strength (%), chemical resistance, flame resistance (UL94, 1. 6 mm) and the evaluation results of the bending strength are shown in Table 3 below. Further, the composition (parts by mass) of each component of the resin compositions of Comparative Examples 2-1 to 2-4, fluidity (g / 10 min), tensile strength (%), chemical resistance, flame resistance (UL94, 1.6 mm) and the evaluation results of the bending strength are shown in Table 4 below.
  • each component to be described is the aromatic polycarbonate resin described in the resin composition of 1st Embodiment which concerns on said this technique, bridge
  • Component A aromatic polycarbonate resin
  • the following components A-1 to A-4 were used as the aromatic polycarbonate resin as the component A.
  • A-1 Commercially available medium molecular weight PC resin (L-1225L: Teijin Chemicals, PS converted Mw 45000).
  • A-2 Commercially available low molecular weight PC resin (L-1225LLL: Teijin Chemicals, Mw 33000 in terms of PS).
  • A-3 PC resin (Mw in PS conversion: 46000) obtained by roughly pulverizing used building material sheets, melting and kneading with a twin screw extruder, and then pelletizing.
  • A-4 Used CD is pulverized (2 to 20 mm) and treated with an alkaline hot water solution to form a coating film (recording material layer, label, adhesive layer, cured layer, metal reflective layer, etc.) After removing, PC resin (Mw in PS conversion: 32000) pelletized after melting and kneading with a twin screw extruder.
  • B component polyurethane resin having a crosslinked structure
  • B-1 to B-3 which are thermosetting resins, were used as the polyurethane resin having a crosslinked structure as the B component.
  • the C-1 component and D-1 component used in the B-3 component are shown below.
  • B-1 Neolabasan N781 (Musashi Paint Co., Ltd.)
  • B-2 Neo Rabasan Soft NS781 (Musashi Paint Co., Ltd.)
  • B-3 having a cross-linked structure obtained by mixing C-1 and D-1 with 100 parts by mass: 100 parts by mass (C-1: D-1) and then reacting by heating at 80 ° C. for 10 minutes. Polyurethane resin.
  • component C polyester polyol
  • component C-1 was used as the polyester polyol as component C.
  • component D polyisocyanate
  • component D-1 The following component D-1 was used as the polyisocyanate as component D.
  • D-1 Duranate TPA-100 (manufactured by Asahi Kasei Corporation).
  • E component organic sulfonic acid and organic sulfonic acid metal salt compound
  • the following components E-1 to E-2 were used as the organic sulfonic acid and organic sulfonic acid metal salt compound as the E component.
  • E-1 organic sulfonic acid metal salt compound, in which potassium sulfonate is introduced into the surface layer of polystyrene (manufactured by Sony Corporation: PSS-K).
  • E-2 Organic sulfonic acid, one obtained by introducing sulfonic acid into the surface layer of polystyrene (manufactured by Sony Corporation: PSS-H).
  • F component anti-drip agent
  • F-1 PTFE commercially available as polytetrafluoroethylene having fibril-forming ability (manufactured by Daikin Industries, Ltd .: Polyflon FA500H).
  • Example 1-1 to Example 1-10 Table 2 (Comparative Example 1-1 to Comparative Example 1-5), Table 3 (Example 2-1 to Example 2-10) and Table 4 (Comparative Example 2) -1 to Comparative Example 2-4)
  • a twin-screw co-rotating extruder Toyo Seiki Seisakusho: Labo Plast Mill, twin-screw
  • Extrusion conditions were a discharge rate of 4 kg / h, a screw rotation speed of 48 rpm, and an extrusion temperature of 270 ° C. from the first supply port to the die part.
  • the obtained pellets were dried in a hot air circulating dryer at 120 ° C. for 8 hours, and then used in the test method shown below at a cylinder temperature of 290 ° C. and a mold temperature of 70 ° C. using an injection molding machine. A test piece was molded.
  • Test method for tensile strength (%)
  • the test piece was subjected to a tensile test according to JIS K7162 method, and the tensile strength was measured.
  • the evaluation results of tensile strength (%) are shown in Tables 1 to 4 below.
  • the bending test is a kind of test for qualitatively evaluating impact resistance by bending a prepared test piece (length: 110 mm, width: 13 mm, thickness: 1.0 mm) and measuring a broken angle. In this evaluation, when the destroyed angle was 90 ° C. or more, it was evaluated as “ ⁇ ”, and when it was within 90 ° C., it was evaluated as “X”.
  • Table 1 shows the results of Examples 1-1 to 1-10, and Table 2 shows the results of Comparative Examples 1-1 to 1-5.
  • the resin compositions according to Examples 1-1 to 1-10 were compatible with thin molded products.
  • the resin compositions according to Examples 1-1 to 1-10 have moldability (fluidity), mechanical properties (tensile strength and tensile strength) as compared with the resin compositions according to Comparative Examples 1-1 to 1-5.
  • the resin composition had excellent bending strength and surface properties (chemical resistance).
  • Examples and Comparative Examples are compared with the same molecular weight of the aromatic polycarbonate resin, that is, Examples 1-1 to 1-3, Examples 1-7 to 1-8, and Comparative Example 1-1 are compared.
  • Examples 1-1 and Comparative Example 1-2 When comparing 1-4 and comparative example 1-2, comparing example 1-5 and comparative example 1-3, and comparing example 1-6 and comparative example 1-4, the example was compared to the comparative example.
  • the mechanical properties tensile strength and bending strength
  • Examples 1-1 to 1-10 were compared with Comparative Example 1-5.
  • Comparative Example 1-5 is a coated product in which a carbonate resin is coated with a polyurethane resin for the purpose of improving chemical resistance.
  • the resin compositions according to Examples 1-1 to 1-10 compared with the resin composition according to Comparative Example 1-5, have a surface physical property (anti-resistance) without reducing mechanical properties (tensile strength and bending strength). Since chemical properties can be imparted, it was excellent.
  • the resin compositions according to Examples 1-1 to 1-10 were very excellent in that the degree of freedom of molding (fluidity) was improved as compared with the resin composition according to Comparative Example 1-5. .
  • Table 3 below shows the results of Examples 2-1 to 2-10, and Table 4 shows the results of Comparative Examples 2-1 to 2-4.
  • the resin compositions according to Examples 2-1 to 2-10 were compatible with thin molded products.
  • the resin compositions according to Examples 2-1 to 2-10 to which organic sulfonic acid or organic sulfonic acid metal salt compound (flame retardant) was added are the same as the resin compositions according to Comparative Examples 2-1 to 2-4.
  • the resin composition was excellent in moldability (fluidity), mechanical properties (tensile strength and bending strength), surface properties (chemical resistance) and flame retardancy.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne une composition de résine présentant d'excellentes propriétés de résine. La composition de résine comprend 100 parties en masse d'une résine de polycarbonate aromatique et 0,01 à 5,0 parties en masse d'une résine de polyuréthane ayant une structure réticulée, et la résine de polyuréthane est une résine durcie.
PCT/JP2018/002183 2017-04-07 2018-01-25 Composition de résine, son utilisation et son procédé de production Ceased WO2018186002A1 (fr)

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CN202210249663.1A CN114634695A (zh) 2017-04-07 2018-01-25 树脂组合物和制备树脂组合物的方法
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JP2023092802A (ja) * 2021-12-22 2023-07-04 三菱エンジニアリングプラスチックス株式会社 難燃ポリカーボネート樹脂組成物
WO2024122493A1 (fr) * 2022-12-06 2024-06-13 三菱ケミカル株式会社 Résine composite, dispersion de résine aqueuse, composition de revêtement et matériau de revêtement à base d'eau

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WO2024122493A1 (fr) * 2022-12-06 2024-06-13 三菱ケミカル株式会社 Résine composite, dispersion de résine aqueuse, composition de revêtement et matériau de revêtement à base d'eau

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